Curable compositions comprising a polymeric bis-cyclopentadienyl compound and a poly-unsaturated material



United States Patent 3,242,112 CURABLE CUMPUSITHQNS CUMPRHSING A POLY- MERHC ltiS-QYCLOPENTADIENYL COMPOUND AND A POLY-UNSATURATED MATERIAL Alfred Renner, Allscliwii, and Franz Rudolf Widmer, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss company No Drawing. Filed Dec. 10, 1962, Ser. No. 243,610 Claims priority, application Switzerland, Dec. 12, 1961, 14,360/61 26 Claims. (Cl. 260-235) The reaction of the bis(cyclopentadienyl) compound a:u'-bis(cyclopentadienyl)-para-xy1ene with N:N'-(1:3- phenylene)-bisma1eimide is known. Even when this re action is performed under very extreme conditions, namely by heating in an autoclave under nitrogen for 48 hours at 200 C., a brittle, insoluble product is obtained which has a softening point of 360 C.

The aforesaid known process is not suitable for the manufacture of curable resin mixtures that can be used, for example, as casting resins, laminating resins or adhesives.

It has now surprisingly been found that when a mixture containing dimeric or polymeric bis(cy-clopentadienyl) compounds and unsaturated dienophilic compounds containing on an average more than 2 nonaromatic carbon-to-carbon double bonds or carbon-to car-bo n triple bonds is heated under normal conditions, cured solid products are obtained that have very valuable technical properties. Such reactive mixtures are, therefore, suitable for a wide variety of uses, for example as casting resins, lacquers, molding compounds, laminating resins and adhesives.

Accordingly the present invention provides a process for the manufacture of cured resins, wherein (1) Dimers or low polymers of bis(cyclopentadienyl) compounds of the general formula in which R stands for a divalent radical, more especially /alkyl aryl Si Si alkyl, aryl or a divalent aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon which may be interrupted by oxygen atoms or substituted by hydroxyl groups or by halogen atoms, 11 is a Whole number from 2 to 20, and R and R each represents a hydrogen atom or a methyl group, are reacted preferably at an elevated temperature with (2) Unsaturated dienophilic compounds having a nonaromatic carbon-to-carbon double bond equivalency and/or carbon-to-carbon triple bond equivalency of which the sum is greater than 2.

As dimeric and polymeric bis(cyc1opentadienyl) com- 3,242,112 Patented Mar. 22, 1966 pounds of the Formula I there are suitable the following compounds in the form of their dimers or oligomcrs:

Bis cyclopentadienyl methane,

Bis cyclopentadienyl) phenylmethane,

1 :5-bis(cyclopentadieny1) pentane,

1 6-bis cyclopentadienyl) hexane,

1 9-bis(cyclopentadienyl)nonane,

l :4-bis (cyclopentadienyl butene-2,

1 :4-bis (cyclopentadienyl) butine-Z,

0c oc'-'blS (cyclopentadienyl apara-xylene,

4: 6-bis (cyclopentadienyl-methyl -l 3dimethylbenzene,

1 3-bis cyclopentadienyl-methyl -2 4 6-trimethylbenzene,

2 2'-bis cyclo pentadieny1)diisopropyl ether,

Biscyclopentadienyl -penteny1] -ether,

1 :4-bis (cyclopentadienyl -cyclo pentene-2,

2: 2'-bis (cyclopent-adienyl-methyl -spiro-di-met=adioxane,

Dicyclopentadienyl dimethylsilane,

Bis (imethyl-cyclopentadienyl) dime thylsilane, and

Di- (cyclopentadienyl) diphenylsilane.

The above-mentioned dimeric or polymeric bis(cyclopentadienyl) compounds are obtained by reacting alkali metal or Grign-ard compounds of cyclopentad-iene or of methylcyclopentadiene with dihalogen compounds of the formula in which R has the same meaning as in Formula I and X stands for a halogen atom, preferably chlorine or bromine and then heating the reaction mixture. When a metal compound of cyclopentadiene or methylcyclopentadiene is reacted, there are (primarily formed the monomeric bis-cyclopentadienes of the formula in which R, R and R have the same meanings as in Formula I.

The monomers are very reactive and are converted, by way of a reaction that often takes place without any intervention, by polydiene addition with themselves into the oligomers or lower polymers. It is of advantage to accelerate this autoreaction by heating to, for example, to C. The oligomeric and low-polymeric products have the character of oils, of viscous liquids or fusible solid resins, depending primarily on the nature of the divalent radical R and on the degree of polymerization 11. In general, the aforesaid products are soluble in suitable solvents, for example in aromatic hydrocarbons or halogen-alkanes. In many cases they constitute mixtures of polymers having different polymerization degrees n. The experimentally determined magnitude of n then represents an average value so that it need not necessarily be a whole number. The values of n as found most often range from 2 to 10. In the case of some structures, for example when R represents CH .CH=CH.CH

(III) the value 12 2 seems to appear most frequently.

When TF2, the experimentally determined molecular Weight and the content of double bonds suggest dimers having a cyclic structure According to the present process bis-cyclopentadienes of the Formula I are reacted with unsaturated dienophilic compounds having a combined non-aromatic carbon-tocarbon double bond or triple bond equivalence greater than 2, that is to say compounds which contain together y non-aromatic carbon-to-carbon double bonds or triple bonds calculated from the average molecular weight, y being a whole or fractional number greater than 2.

When the aforesaid unsaturated dienophilic compounds (2) represent unitary chemical substances that can be defined by a structural formula, their molecules must contain at least 3 non-aromatic carbon-to-carbon double bonds and/ or carbon-to-carbon triple bonds. In many cases of special practical importance-such as the unsaturated polyesters or the copolymers of butadiene these products are known as mixtures of compounds of different molecular Weights and a different content of double bonds, so that in each case the experimentally determined value of the double bond and triple bond equivalence is an average value. The double bond and/ or triple bond equivalence of such unsaturated products need therefore not necessarily be a whole number greater than 2, but it must always be greater than 2.

As such unsaturated dienophilic compounds (2) having an olefinic double bond and/or triple bond equivalence greater than 2, there are especially suitable the following types of compounds:

(a) Unsaturated polyesters from unsaturated dicarboxylic or polycarboxylic acid with glycols or polyols, which may be modified with saturated dicarboxylic or polycarboxylic acids. As unsaturated polycarboxylic acids, from which such polyesters are derived, there may be mentioned: Maleic, fumaric, mesaconic, citraconic, itaconic, tetrahydrophthalic and aconitic acid.

As glycols or polyols, from which such unsaturated polyesters may be derived, there may be mentioned: Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol-1:2, propylene glycol-1:3, butanediol- 1:4, 2-methylpentanediol-2:4, pentanediol-125, hexanediol-1z6; bis-fl-hydroxyethyl ethers of bisphenol A (2:2'- bis[para-hydroxyphenyl]propane) or of tetrachloro-bisphenol A; glycerol, diglycerol, trimethylolethane, trimethylolpropane, butanetriol-(1z2z4); hexanetriol, pentaerythritol and pentachlorophenyl-glycerol ether.

As saturated dicarboxylic or polycarboxylic acids, which, if desired, may be concomitantly used to modify the unsaturated polyesters, there may be mentioned, for example: Oxalic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, hexahydrophthalic, tricarballylic, phthalic, isophthalic, terephthalic, 2:6-naphthalene-dicarboxylic, diphenyl orthozortho' dicarboxylic acid, ethylene glycol-bis(para-carboxyphenyl)ether tetrach1o 4 ro-phthalic, hexachloroendomethylene-tetrahydrophthalic and tetrachlorosuccinic acid. (b) Unsaturated polyesters from unsaturated dihydric or polyhydric alcohols with unsaturated dicarboxylic or polycarboxylic acids which, if desired, may be modified by saturated dihydric or polyhydric alcohols and/ or saturated dicarboxylic or polycarboxylic acids.

As unsaturated polyols from which such polyesters may be derived there may be mentioned:

1 6-bis (hydroxymethyl) -2 5-endomethylene-cyclohexene-3,

1 1-bis(hydroxymetl1yl) cyclohexene-3, and

1 1-bis(hydroxymethyl)-6-methyl-cyclohexene-3.

As unsaturated polycarboxylic acids and optionally also used saturated polycarboxylic acids and saturated polyalcohols there may be used for the synthesis of the unsaturated polyesters referred to under (b) above the compounds referred to under (a) above.

(0) Esters from monobasic unsaturated monocarboxylic acids, such as acrylic, methacryl-ic, crotonic, cinnamic, furfuracrylic, oleic, linoleic, ricinoleic or soybean fatty acid, with trihydric or polyhydric alcohols, such as glycerol, trimethylolpropane, pentaerythritol, hydroxyethylated or hydroxypropylated novolaks, polyglycerol ethers of polyhydric phenols. As examples the following compounds may be mentioned:

Glycerol-trisacrylate, glycerol-trisoleate and unsaturated natural vegetable and animal oils, such as linseed oil, tung oil or fish oils.

(d) Esters from unsaturated dicarboxylic or polycarboxylic acids, such as maleic, fumaric or itaconic acid, and unsaturated monohydric alcohols, such as allyl alcohol or crotyl alcohol. As examples there may be mentioned diallyl maleate and dicrotyl maleate.

(e) Ethers from unsaturated monohydric alcohols, such as allyl or crotyl alcohol, and compounds containing three or more hydroxyl groups, such as glycerol, pentaerythritol, methylolmelamines or cyanuric acid. As relevant examples there may be mentioned hexamethylolrnelamine pentaal-lyl ether, a transetherification product, containing on an average more than 2 alloxyethyl groups per molecule, from hexamethylolmelamine hexamethyl ether and ethylene glycol monoallyl ether, or triallyl cyanurate.

(f) Polymers and copolymers of dienes, such as butadiene or isoprene, whose molecule contains on an average more than 2 carbon-to-carbon double bonds. Particularly suitable copolymers are those of butadiene or isoprene with ethylene, propylene, styrene, acrylonitrile or acrylic acid esters, such as ethyl acrylate or butyl acrylate. Typical representatives of this group of compounds are marketed, for example, under the registered trademark Buton resins.

(g) Compounds which are derived from carboxylic acids having a carbon-to-carbon triple bond, such as a propargylic or acetylenedicarboxylic acid, and which contain on an average a total of more than 2 carbon-to-carbon double bonds and triple bonds per molecule. Suitable examples are esters of acetylenedicarboxylic acid with monohydric unsaturated alcohols, for example diallylacetylenedicarboxylate, also esters of propargylic acid with at least trihydric alcohols, for example glycerol-trispropargylate, and finally unsaturated polyesters derived from acetylenedicarboxylic acid and the diols or polyols listed under (a) above, or from other unsaturated and/or saturated dicarboxylic or polycarboxylic acids likewise listed under (a) above.

The curing reaction according to the invention taking place between the bis(cyclopentadienyl) compound of the Formula I and the unsaturated dienophilic compounds having a non-aromatic double bond or triple bond equivalence greater than 2 is advantageously performed at an elevated temperature, preferably at a temperature ranging from to 200 C. This curing reaction is probably based on the following reaction mechanism: As is known, drcyclopentadiene is pyrolyzed to monomeric cyclopentadiene at a temperature above 150 C. With dienophilic compounds, for example maleic anhydride, on the other hand, monomeric cyclopentadiene reacts at such elevated temperatures with formation of the much more stable, so-called Diels-Alder adduct. Therefore, the curing reaction of the invention performed at an elevated temperature is probably accompanied by a depolymerization of the dimeric or polymeric bis(cyclopentadienyl) compound in the presence of the unsaturated dienophilic compound (2) with which the monomeric bifunctional scission products-which have been formed in situ and are very short lived under the reaction conditionsimmediately undergo a further reaction. Since the molecule of the unsaturated dienophilic compound contains on an average more than 2 double or triple bonds, the reaction leads to three dimensional cross-linking.

At room temperature the curable mixtures of the dimeric or low-polymeric bis(cyclopentadienyl)compound and the unsaturated dienophilic compound are at least sufiiciently stable to enable their industrial use as casting resins, laminating resins, adhesives or the like. Whereas, for example, mixtures containing dimeric or trimeric paraxylylene-biscyclopentadiene have only a very limited pot life, those mixtures which contain dimeric 1:4-bis(cyclopentadienyl)-butene-2 are especially distinguished by an outstanding pot life and shelf life and can be stored almost indefinitely at room temperature.

The fact mentioned above is of considerable industrial importance because it makes it possible to manufacture storable, heat-curable one-component systems which may be used, for example, as casting resins, lacquers, laminating resins, moulding compounds or adhesives.

It is also possible to interrupt the reaction of the polymeric bis(cyclopentadienyl) compound with the unsaturated dienophilic compound, for example, by quenching the reaction mixture before the cross-linking is complete. In this manner it is possible to produce prepolymers, similar to the so-called B-stages in the case of phenolformaldehyde resins which can still be shaped and cured at an elevated temperature and are especially suitable for certain purposes, for example for the production of mouldings or laminates.

When suitable catalysts are used, for example metal driers such as cobalt naphthenate or cobalt octoate, while at the same time providing an atmosphere of oxygen, the curing may also be performed at room temperature. Such systems, which cure even when no external heat is supplied, may be used, for example as cold-curing or airdrying lacquers.

As a rule, cross-linked infusible products of any desired shape may be manufactured by means of various techniques to yield casting, foamed products, mouldings, surface coatings, laminates, glued objects and the like. In this method a curable mixture of the starting components (l) and (2) and optionally the concomitantly used catalyst is prepared, filled into casting or press moulds, or brushed on as coatings, or introduced into joints to be cemented or the like, and the mixture is then allowed to cure, advantageously while applying external heat. Instead of a mixture of the components 1) and (2) there may be used a curable precondensate of these two substances.

The term curing as used in this context signifies the conversion of the aforesaid starting components (1) and (2), or of their precondensates, into insoluble, infusible resins.

Accordingly, the present invention includes within its scope curable resin mixtures containing (1) A bis(cyclopentadienyl) compound of the Formula I,

(2) An usaturated dienophilic compound having a nonaromatic carbon-to-carbon double bond equivalence and/ or carbon-to-carbon triple bond equivalence greater than 2; or a curable precondensate obtained from the components (1|) and (2), and, if desired,

(3) A catalyst, for example a metal drier.

As active diluents the curable mixtures of the invention may further contain unsaturated compounds containing 1 or 2 non-aromatic carbon-to-carbon double or triple bonds, such as styrene, diallyl phthalate or glycolbis-methacrylate.

It is further possible to add to the curable mixtures of the invention curable resins, for example phenoplasts, polyacetals from polyalchohols and aldehydes, or epoxy resins, provided they are compatible with the aforesaid components 1) and (2) and can be cured under the curing conditions employed together with the said components.

There may further be added to the curable mixtures at any stage prior to the curing operation fillers, plasticisers, pigments, dyestuffs, mould lubricants, flame-inhibitors or the like. Suitable extenders and fillers are, for example, asphalt, bitumen, glass fibers, mica, quartz meal, cellulose, kaolin, colloidal silicon dioxide having a large specific surface (Aerosil) or metal powders.

The curable mixtures of the invention. may be used in the unfilled or filled state, if desired in the form of solutions or emulsions, as textile auxiliaries, laminating resins, moulding compounds, injection moulding compounds, paints, lacquers, dipping resins, casting resins, coating compositions, pore fillers, putties, adhesives or the like and also for the manufacture of such products. By virtue of their good film-forming properties and the outstanding adherence of the cured products on substrata, such as glass, porcelain, metals, wood, masonry and the like the curable mixtures of the invention are of special value for the protection of surfaces and as adhesives.

Parts and percentages in the following examples are by weight, and the relationship between part by weight and part by volume is the same as that between the kilogram and the liter.

The curing reactions described in the following examples were performed with the following bis (cyclopentadienyl) compounds I-XVI and the following unsaturated compounds (polyesters A to F and hexamethylolmelamine pentaallyl ether G):

(a) BIS(CYCLOPENTADIENYL) COMPOUNDS I. Polymeric I:5-bis(cyclopentadienyl)penzane.-ll0 parts of sodium metal are fused in 875 part of xylene, finely dispersed and then cooled. 20 parts of tertiary butyl alcohol and 1.5 parts of tertiary butyl catechol are added and while cooling externally 370 parts of monomeric cyclopentadiene are stirred in dropwise at 45 C. The batch is left to itself for 14 hours at 20 C. under nitrogen. At 50 to 55 C. 460 parts of 1:5-dibromopentane are added and the mixture is stirred for another 2 hours at C. Titration of the bromine ions reveals that a quantitative conversion has occurred. The batch is cooled to room temperature, mixed with 80 parts of methanol and 1000 parts of water and neutralized with 30 parts of acetic acid, then thoroughly mixed, and the aqueous layer is separated and the xylene solution is dried over sodium sulfate and filtered. The xylene is distilled off under 15 mm. Hg pressure and the reaction product is kept under this pressure for 3 hours at C.

Yield: 390 parts of polymeric 1:5-bis(cyclopentadi enyl)-pentane 97.5% of the theoretical yield) in the form of a light-brown resin which is just still liquid at IOOIII temperature.

II. Dimeric J:4-bis(cycl0pen2adienyl)Jmtene (2).- While cooling externally a suspension of cyclopentadienyl sodium prepared as described above under I from 2080 parts of xylene, 276 parts of sodium, 35.5 parts of tertiary butanol, 0.5 part of phenyl-B-naphthylamine and 872 parts of cyclopentadiene, 712 parts of 1:4-dichloro-butene-(2) are stirred in at 30 to 35 C, The temperature is then raised and maintained for 3 hours at 105 C. Titration of the alkalinity reveals that a quantitative conversion has taken place. The batch is filtered at room temperature and the sodium chloride formed is washed with x 400 parts of xylene. The xylene is evaporated under a pressure of mm. Hg and the residue is kept for 1 hour at 100 C. 1 mm. Hg pressure.

Yield: 978 parts of dimeric 1:4-bis(cyclopentadienyl)- butene-(Z) 93.2% of the theoretical yield calculated from 1:4-dichlorobutene-(2)] in the form of a light-brown III. Polymeric 4:6 bis(cyclopentadienyl-methyl)-1:3- dimetlzylbenzene.While externally cooling a suspension of cyclopentadienyl sodium (prepared as described under I from 345 parts of xylene, 46 parts of sodium, 5.9 parts of tertiary butanol, 0.5 part of tertiary butylcatechol and 158 parts of cyclopentadiene) diluted with 100 parts of ethyleneglycol diethyl ether, a solution of 193 parts of 4:6- bis-(chloromethyl)-1:3-dimethylbenzene in 500 parts of xylene is stirred in at 50 C. The temperature is raised and maintained for 2 hours at 130 C. The sodium Chloride formed is filtered off at room temperature and washed with xylene. The solvent is evaporated under 15 mm. Hg pressure and the residue is kept for 4 hours under same pressure at 90 to 100 C.

Yield: 199 parts of polymeric 4:6-bis-(cyclopentadienyl-methyl)-l:3-dimethylbenzene [=80% of the theoretical yield calculated from the initially used 4:6-bis-(chloromethyl)-1:3-dimethylbenzene], as a brown, brittle resin.

IV. Polymeric 1:3-bis(cyclopentadienyl-methyl)-2:4:6- trimethylbenzene.-While externally cooling a suspension of cyclopentadienyl sodium (prepared as described under III), diluted with 100 parts of ethyleneglycol diethyl ether, a solution of 206 parts of 1:3-bis-(chloromethyl)- 2:4:6-trimethylbenzene in 605 parts of xylene is stirred in at to C. The temperature is then slowly raised to 105 C. and kept at this level for 4 hours. The sodium chloride formed is filtered oil at room temperature and washed with 3 x 173 parts of xylene. The filtrate is concentrated under 18 mm. Hg and finally kept for 1 hour at 90 C. under the same pressure. A quantitative yield is obtained of a light-brown, brittle resin having a softening point of 84 C. (on the Kofler hot bench).

C, percent H, percent Molecular weight Analysis:

Calculated for (02111101 91. 3 8. 7 Found. 89.1 8.6 756 pentenyl)ethers [bis(5 chloro 3-pentenyl)ether+bis(3 chloro-4-pentenyl)ether] in 87 parts of xylene are stirred in at 30 to 33 C. The temperature is then maintained for 14 hours at 50 C. and then for 3 hours at C. The sodium chloride formed is filtered oil at room temperature and Washed with 3 x 40 parts of Xylene. The solvent is distilled oil under a pressure of 18 mm. Hg and the residue is kept for 2 hours at 90 C. under 0.1 mm. Hg pressure. Yield: 101 parts of a brownish red oil.

The mixture of isomers of bis(chloropentenyDethers can be prepared, for example, by the process described in German specification No. 862,154 of January 8, 1953, to Rohm & Haas Company, Philadelphia, Pa. (V. St. A.), from 1 molar proportion of symmetrical dichlorodimethyl ether and 2 molar proportions of butadiene.

VI. Dimeric 1:3 bis(cyclopentadienyl)-pr0pan0l-2. As described under I a suspension of cyclopentadienyl sodium in xylene is prepared from 875 parts of xylene,

parts of sodium,

20 parts of tertiary butanol,

1.5 part of tertiary butylcatechol, and 363 parts of cyclopentadiene.

While cooling this suspension 231 parts of epichlorohydrin are stirred in at a rate such that the temperature of the reaction batch remains constant at 30 C. The batch is kept for 15 hours at room temperature and then mixed, while being cooled, with 247 parts of concentrated hydrochloric acid (of 37% strength). The aqueous phase is separated, washed with 250 parts of water, dried over sodium sulfate, filtered, and the solvent is evaporated in a falling-film evaporator at C. under 15 mm. Hg pressure.

Yield: 248 parts of a dark-red substantially solid resin.

Calculated for dimeric dicyclo- Found peutadienylpropanol- (2) Molecular weight 376 370 Active hydrogen, percent. 0. 53 0. 52

VII. Dimeric di cyclopentadienyl-dimethylsilane.AS described under I a suspension of cyclopentadienyl sodium is prepared from 875 parts of xylene,

115 parts of sodium,

20 parts of tertiary butanol,

1.5 parts of tertiary butylcatechol, and 363 parts of cyclopentadiene.

Calculated Found Analysis:

Molecular Weight 376 390 Silicon, percent 14.9 14 3 VIII. Dimeric eli-(x-methylcyclopentadienyl)-dimcthyl silane.-The method used is that described under VII, except that the 363 parts of cyclopentadiene are replaced by 440 parts of methylcyclopentadiene (boiling at 70 C.) prepared by pyrolysis of commercial dimethyldicyclopentadiene. Yield: 258 parts of a light-yellow oil having a molecular weight of 366.

are stirred in dropwise.

IX. Oligomeric bis(cyclpentadienyl)methane-As described under I a suspension of cyclopentadienyl sodium in xylene is prepared from 1820 parts of xylene,

230 parts of sodium,

30 parts of tertiary butanol,

1 part of phenyl-B-naphthylamine, and 726 parts of monomeric cyclopentadiene.

The suspension is heated to 90 C. and, while heating the batch, 383 parts of methylene chloride are stirred in dropwise within hours at l00-120 C., after which the mixture is heated for 3 hours at 110 to 120 C., then cooled to room temperature, neutralized with glacial acetic acid, the sodium chloride formed is filtered off and the filter cake is washed twice with xylene. The solvent is evaporated under vacuum, finally at 90 C. under 18 mm. Hg pressure. Yield: 465 parts (=72% of the theoretical) of trimeric bis(cyclopentadienyl)methane in the form of a light-brown, plastic resin.

X. Oligomeric 1:4 bis(cycl0pentadz'enyl) butz'ne-(2).-- While externally cooling a suspension of cyclopentadienyl sodium (prepared as described under I from 175 parts of xylene, 23 parts of sodium, 3 parts of tertiary butanol, 0.05 part of phenyl-B-naphthylamine and 72.6 parts of monomeric cyclopentadiene) a mixture of 58.4 parts of 1:4-dichlorobutine-(2) in 20 parts of tetrahydrofuran is stirred in within 40 minutes at 30 C. The batch is then heated to 90 C. and kept at this temperature for 2 hours, then neutralized with acetic acid; the sodium chloride formed is filtered otf, washed twice with xylene, and the solvent is distilled off from the filtrate under reduced pressure, finally for 1 hour at 80 to 100 C. under a pressure of =18 mm. Hg. Yield: 45 parts of polymeric 1:4-bis(cyclopentadienyl)-butine-(2) in the form of a brown, viscid liquid. Molecular weight: 257.

XI. Oligomeric bis(cyclopentadienyl)phenylmethane.- 23 parts of sodium are fused in 87 parts of xylene, finely dispersed and cooled. 56 parts of xylene are decanted and replaced by 180 parts of tetrahydrofuran. 3 parts of tertiary butanol and 0.05 part of phenyl-fi-naphthylamine are then added, the whole is heated to 60 to 75 C., and in the course of 35 minutes 76.5 parts of benzalchloride The reaction mixture is refluxed for 2 hours, cooled to room temperature, neutralized with glacial acetic acid, and the sodium chloride formed is filtered off. The filter cake is washed 3 times with xylene. The filtrate is evaporated under reduced pressure, finally for 2 hours at 95 C. under 18 mm. Hg pressure. Yield: 82.5 parts (=79% of the theoretical) of a brownish red, brittle resin which turns soft at 107 C. (on a Kofler hot bench). Molecular weight: 633.

XII. Oligomeric 2:2'-bis(cyclopentadienyl)diisop ropyl ether.This compound is prepared as described under XI from 54 parts of xylene, 46 parts of sodium, 5.9 parts of tertiary butanol, 145 parts of cyclopentadiene and 168 parts of 2:2-dichloro-diisopropyl ether, the latter being added to the solution of cyclopentadienyl sodium at 40 C. After conventional processing 189 parts (=83.6% of the theoretical yield) of a reddish brown, thickly liquid oil are obtained. Molecular weight: 366.

XIII. Polymeric 2:2-bis(cyclopentadienyl-methyl)-spir0-bi-metadi0xane.-69 parts of sodium are fused in 250 parts of xylene, finely dispersed and cooled. By repeated decantation and addition of tetrahydrofuran the xylene is replaced by 400 parts of tetrahydrofuran. 15 parts of tertiary butanol are added and then, at 35 C., 218 parts of monomeric =cyclopentadiene. The solution is stirred for 16 hours at room temperature. A solution of 257 parts of pentaerythritol-bis(chloracetaldehyde)acetal in 300 parts of tetrahydrofuran is added dropwise within 1 hour at 65 to 70 C., the temperature is maintained for 2 hours at 65 C., and the batch is then cooled. The sodium chloride formed is filtered off and washed With tetrahydrofuran. The filtrate is evaporated under reduced pressure, finally for 45 minutes at 70 C. under 0.8 mm. Hg pressure. Yield: 275 parts (=81.3% of the theoretical) of a light-brown, clear, soli-d resin. Softening point: 54 C. (on a Kofler hot bench).

XIV. Dimeric di cyclopentadienyl dip/lanylsilund- While externally cooling a suspension of cyclopentadienyl sodium prepared as described under I from 2100 parts of xylene, 276 parts of sodium, 48 parts of tertiary butanol, 3.6 parts of tertiary butylcate-chol and 871 parts of cyclopentadiene, 1518 parts of diphenyldichlorosilane are stirred in dropwise at 30 C., and the mixture is kept for another 3 hours at 30 C., then neutralized with glacial acetic acid; the sodium chloride formed is filtered off and washed with xylene. The solvent is evaporated under reduced pressure, finally for 30 minutes at 65 C. under 0.5 mm. Hg pressure. Yield: 1440 parts =77% of the theoretical) of a light-brown, solid resin. Softening point: 66 C. (on a Kofler hot bench).

Molecular weight:

Calculated for the dimer 625 Found for the dimer 555 XV. Oligomeric 1:4-bis(cyclopentadienryl)cyclopentene- (2).While externally cooling a solution of cyclopentadienyl sodium (prepared as described under XIII from 80 parts of xylene, 1 80 parts of tetrahydrofuran, 23 parts of sodium, 3 parts of tertiary butanol, 0.1 part of phenyl-[i-naphthylamine and 72.6 parts of cyclopentadiene), 107 parts of 1:4-dibromocyclopentene-(2) are stirred in dropwise within 30 minutes at 30 C. The mixture is stirred for 16 hours at room temperature, then neutralized with glacial acetic acid, the sodium bromide formed is filtered off and washed with tetrahydrofuran. The filtrate is heated for 2 hours at 80 C., then concentrated under vacuum, finally for 1 hour at 40 C. under 0.1 mm. Hg pressure. Yield: 79 parts of a viscid, dark brown oil. Molecular weight: 643.

XVI. Copolymer from 1:4-bis(cyclopentadienyl)-butene-(Z) and 2.'2'-bis(cycl0pentaaienyl)dielhyl ether.- The above copolymeric bis(cyclopentadienyl) compound is prepared in the same manner as the bis(cyclopentadienyl) compound XIII from 320 parts of xylene, 152 parts of sodium, 1200 parts of tetrahydrofuran, 30 parts of tertiary butanol, 0.3 part of phenyl-B-naphthylamine, 475 parts of cyclopentadiene, 214 parts of B-dichlorodiethyl ether and 187.5 parts of 1:4-dichlorobutene. The viscid resin has a molecular weight of 784.

(b) UNSATURATED COMPOUNDS Unsaturated polyeszer A.A mixture of 1245 parts of isophthalic acid, 22 parts of phthalic anhydride, and 1435 parts of 1:2-propylene glycol is esterified under nitrogen at to 210 C., while dis .tilling off the water of reaction, in an apparatus com- .prising a column and a descending condenser until the acid number is smaller than 5881 parts of maleic anhydride are then added and the batch is esterified at 200 to 220 C. until an acid number of 25 has been established. Yield: 3300 parts of a solid resin softening at 65 C. (on a Kofler hot bench); it displays a double bond equivalence of 2.74 .per kg. and has an average molecular weight of 1930.

1 1 Unsaturated polyester E.A mixture of 5 88 parts of maleic anhydride,

655 parts of neopentyl glycol (=2z2-dirnethylpropanediol-1z3), and

0.25 part of hydroquinone is esterified at 160 to 200 C. under nitrogen, and while distilling off the water of reaction, until an acid number of 35 has been reached. There are obtained 1136 parts of a resin which is still soft at room temperature; it displays a double bond equivalence of 5.8 per kg. and has an average molecular weight of 2260.

Unsaturated polyester G.A mixture of is esterified for 36 hours while removing the water of reaction azeotropically; a total of 100 parts of water is removed. After the toluene has been distilled off, there are obtained 1528 parts of polyester resin which displays a double bond equivalence of 2.62 per kg, contains 27.9% of chlorine and has an average molecular weight of 1940.

Unsaturated polyester D.A mixture of 1160 parts of fumaric acid, 836 parts of 1:2-propylene glycol, and 1 part of hydroquinone is esterified for 9 hours at 148 to 226 C. under nitrogen in an apparatus comprising a column and a descending condenser, a total of 347 parts of water being removed. During the last 90 minutes of the esterification the reaction is performed under reduced pressure (100 to 18 mm. Hg). Yield: 1621 parts of a solid polyester resin displaying a double bond equivalence of 6.17 per kg., having an average molecular weight of 2800 and an acid number of 27.

Unsaturated polyester E.A mixture of 91.2 parts of acetylenedicarboxylic acid, 223.3 parts of bis(2-hydroxyethyl)isophthalate, 3.14 parts of para-toluenesulfonic acid and 950 parts of benzene is subjected to an azeotropic distillation until water no longer separates. The solvent is evaporated under vacuum, finally for 3 hours at 100 to 125 C. under 0.1 mm. Hg pressure, to yield 215 parts of a solid resin. Softening point: 48 C. (on a Kofler hot bench). Acid number: 17.5.

Unsaturated polyester F.A solution is prepared by heating a mixture of 129.1 parts of ethylene glycol, 339.5 parts of diethylene glycol, 156.9 parts of maleic anhydride, 355.5 parts of phthalic anhydride, 116.9 parts of adipic acid, and

0.1 part of hydroquinone.

The solution is heated under nitrogen to 200 C. and esterified for 3 hours under atmospheric pressure while separating the water formed. The batch is then further esterified under reduced pressure for 5 hours at the same temperature until the polyester has reached an acid number of 17. Yield: 989 parts of a viscous liquid, having a double bond equivalence of 1.62 kg. and an average molecular weight of 3010.

H examethylolmelamine pentaallyl ether G.A mixture of 648 parts of hexamethylolmelamine, 2580 parts of allyl alcohol and about 237 parts of hydrochloric acid of approximately 36% strength is vigorously stirred for 1 hour at 25 C. in a fiask, then neutralized with calcined sodium carbonate (about 235 parts) to brilliant yellow-orange red. The salt formed is then filtered off and washed with allyl alcohol. A mixture of allyl alcohol and water is then distilled off the clear filtrate under a pressure of about 400 mm. Hg. The batch is then totally dehydrated by being heated in an oilbath at an internal temperature of about 105 C. under diminished pressure. The turbid syrup is allowed to stand for a few hours and then filr tered while cold, to yield 883 parts of a water-clear syrup consisting substantially of an allyl ether which contains about five allyl ether groups for every molecular proportion of melamine.

Example 1 Mixtures of casting resins are prepared by intimately mixing a bis(cyclopentadienyl) compound II, V or VI with an unsaturated polyester A, B, C or D and in two specimens additionally with still another unsaturated compound in one of the ratios shown in the following Table I at 100 to 140 C. and, if necessary, degassing the mixture. The casting resin specimens are cast in aluminum moulds (140 x 40 x 10 mm.) and cured in an air-drying oven under the curing conditions shown in Table I. The mechanical properties of the cured castings are likewise listed in Table I.

TABLE I Curing conditions Properties of the cured castings Polymeric bis Additional Specimen (dicyelopenta- Unsaturated unsaturated Prelim. Final Modulus Heat distor- N dienyl) compolyester compound curing curing Flexural Impact of elastion point pound strength, strength, ticity, accdg. to kg./mm. 0m.kg./cm. cgJmm. Martens Hrs. 0. Hrs. C. (DIN), C.

2 150 24 180 10. 6 6. 7 579 1 130 24 180 10.5 9. 3 633 61 2 150 24 180 8. 8 6. 4 593 2 150 24 180 9. 7 7. 9 540 73 2 150 24 180 11.1 4. 7 666 61 24 150 24 180 10. 5. 8 559 99 a 150 24 180 9. 5 6.8 564 as a 2 150 5 180 5. 2 8.8 589 62 2 150 5 180 12. 5 2. 7 713 87 2 150 5 180 8. 2 7. 8 528 48 2 150 5 180 6. 6 5. 2 51 2 150 5 180 8.9 9. 4 51 bismethacrylatc. 13 II M 34 A 100 Diallyl 6 2 5 10.2 6, 9 55 malcate.

1 The cured specimen 9 is self-extinguishing (combustlbility accdg. to VDE 0303=Stage I, burns for 2 seconds).

13 Example 2 100 parts each of unsaturated polyester A are mixed with the amounts shown in the following Table II of the polymeric bis(cyclopentadienyl) compounds II, III, IV, VII or VIII and diluted with chloroform (100 to 120 parts of chloroform for every 100 parts of dry substance). Glass fiber fabrics are impregnated with the solutions thus prepared and then dried in air for V2 to 1 hour. The fabrics are then further dried in an air-drying oven at amounts of still unsaturated compound, and each resulting mixture is diluted with chloroform to form adhesive cements having a solids content of 50%.

Aluminum sheets marketed under the registered trade name Anti-corodal B (17 x 25 x 1.5 mm; mm. overlap) are brushed with the cements, allowed to dry in air, clamped and cured for 5 hours at 180 C. in an air-drying oven. The shear strength values of the bonded sandwiches found at room temperature are shown in Table III.

TABLE III Polymeric bis(cye1o- Additional unsaturated Shear Specimen N0. pentadienyl) Unsaturated polyester compound strength, compound kgJmm.

100 Diallylmaleate 18 3.38

100 Glycolbis-meth- 27 2.88

acrylate.

100 Maleic acid di- 35 0.90

propargyl ester. 100 1.0 100 1.5

an elevated temperature under the conditions listed in Example 4 Table II. The fabric specimens are then cut up into squares x 15 cm.), 12 to such sheets are stacked and then cured to form a laminate in a heated press under the pressing conditions shown in Table II. The properties of the laminates are likewise shown in Table II.

Mixtures of one of the bis(cyclopentadieny1) com- 35 pounds I, II, III, v11 or VIII with the unsaturated poly- TABLE II Conditions for drying the im- Polymeric bis- Parts per 100 pregnated glass fabric in an Pressing conditions, Preliminary pressing Specimen (cyclopentadipts. of unsatuair-drying oven No, enyl) rated polyester compound A Mins. 0. Mins. 0. Press,

kg./cm.

Pressing conditions, Final Properties of the laminates pressing Specimen Flexural strength Heat distor- Water ab- N1), tion point sorption after Press, Impact accdg. to 1 hour at Mins. C. lrgJcm. After 1 hour strength, Martens 100 C. in

Thickness of Dry, in water at cm.kg./cm. (DIN) in percent laminat kgjmrh. 100 0., 0.

mm. kg./mrn.

Example 3 form to form lacquer solutions having a solids content of 100 parts each of unsaturated polyester A, E or F are mixed with the amounts shown in the following Table III of the polymeric bis (cyclopentadienyl) compounds I, IV, V, VI, VII, VIII, X, XI, XIII, XIV or XV and three 25%. Two of the lacquer specimens mixed with linseed oil are catalysed with a solution of 1% strength of cobalt octoate in toluene. Aluminum sheets 0.4 mm. thick are brushed with the lacquer specimens thus prepared, allowed to dry in air for /2 hour and then cured in an air-drying specimens are additionally mixed with the indicated oven under the condition shown in Tabl IV, The o erties of the cured lacquer films are likewise shown in Example 6 Table IV. Mlxtures of a b1s(eycl0pentad1enyl) compound I, XIII TABLE IV Curing in air drying Properties of the lacquer Cobalt cabinet fihns Specimen Polymeric bis(cyc1o- Unsaturated dienophilie metal (as No. pentadienyl) compound compound Co-octoate),

parts Stability Time, mins. Temp, C. towards Adhesivity 2 acetone Parts Parts II 21.6 Polyester A 100 60 250 1 Good. III 36 d 60 250 1 Do. VII 26 60 250 1 Do. VIII 29 60 250 1 Do. 72 60 160 3 Do. I 72 60 160 2 Do. II 69 60 I60 1 D0, II 69 60 160 2 Do,

1 The lacquer surface is rubbed ten times to and fro with a swab of eottonwool impregnated with acetone, and the results observed are classified as follows:

1=Laequer surface displays no visually noticeable damage.

2=Surface slightly turbid.

3=Surfaee strongly attacked.

4=Laequer film detached.

2 After having been folded twice (as a sheet of paper is folded in half and then again at right angles to the first fold) the lacquer film should still adhere to the metal sheet.

25 or XIV with the unsaturated polyester A or E or with Example 5 hexamethylolrnelamine pentaallyl ether G in the amounts Lacquer Solutions are P pared by 'g thfi Y shown in the following Table VI are diluted with the p y compound II with a styl'enfi-blltadiene amounts of sol-vent shown in Table VI to form lacquer P y (marketed under the registered trade name solutions. Aluminum sheets 0.4 mm. thick are brushed ton 100, which is free from solvent, has an average molecwith the lacquer specimens thus prepared, allowed to dry ular weight of 8,000 to 10,000 and an iodine number of in air for /2 hour and then cured in an air-drying oven about 300), and by dilution with benzene in the ratios under the conditions shown in Table VI. The properties shown in the following Table V. The lacquer solutions of the cured lacquer films are likewise shown in Table thus prepared are brushed on aluminum sheets and cured VI.

TABLE VI Curing in air Properties of the drying cabinet lacquer films methyl Polymeric bis Unsaturated dieno Solvent isobutyl Stabim Specimen (cyclopentadienyl) philie compound Other additives xylene, ketone, g' Adhe- N0. compound parts parts Time, Temp, aceumel sivity mins. C.

(see explanation to Table IV) Parts Parts Parts 1 I 52 Hexamethyl- 100 75 25 60 150 1 Very good.

olmelaminepentaallyl ether. 2 XIII 43.4 Polyester E 100 162 54 10 180 1 Good. 3 XIII 87 do 100 Bllflan 250 82 10 180 1 Very'good.

1 4 XIV 43 Polyester A. 100 71 24 30 180 1 Good. 5 XIV 66 Hexamethyl- 100 133 33 30 180 1 D0.

olrnelaminepentaallyl ether.

1 See footnote 1 of Table IV. 1 See footnote 2 of Table IV. 3 See Example 5.

under the conditions shown in Table V. The properties of the cured lacquer films are likewise shown in Table V.

' TABLE V Curing in air Properties of the lacquer Parts of polydrying cabinet films Specimen merie bis Parts of Parts of N0. (cycle enta- Buton 100 benzene dienyl com- 7 7 H Time, Temp, Stability pound'II mins. 0. towards Adhesivity 1 aeetone 96 85 543 10 180 2-3 Good.

96 85 543 20 180 2 Do; 96 85 543 180 1 D0. 48 399 10 2 D0. 48 85 399 20 188 2 D0. 48 85 399 G0 180 1 D0.

1 See footnote 1 of Table IV. 1 See footnote 2 of Table IV.

Example 7 A mixture of 912 parts of unsaturated polyester A dissolved in 304 parts of ethylene chloride,

171 parts of bis(cyclopentadienyl) compound II [dimeric 1 :4-bis cyclopentadienyl -butene-2] 95 parts of tertiary butylperbenzoate of 50% strength in dibutyl phthalate,

50 parts of zinc stearate,

600 parts of kaolin,

150 parts of titanium dioxide, and

750 parts of glass fibers of 6 mm. length is kneaded in a Werner-Pfieiderer kneader for 20 minutes and then dried for 8 hours in a vacuum cabinet at 60 C. The dried material is ground in a cutting mill through a mm. sieve to form a granulate which is then molded under a pressure of 2010 k g/cm. to form shaped products.

Molding conditions Properties Time, Temperaminutes ture, C.

6 165 Flexural strength, 407 kglcmfl. 6 r 165 Impact strength, 5.5 cm. kg./

cm. 6 165 Notched bar impact strength,

6.4 cm. kg./e1n. 6 165 Heat distortion point accdg. to

Martens (DIN), 45 0. 3. 25 165 Glow strength (V DE), grade 3. 3 165 Dielectric loss factor tga (50 gyglgs at 1,000 volt; VDE), 3 165 Dielectric constant e (50 cycles at 1,000 volt; VDE), 6.4. 3 165 Specific resistance VDE, 7.3 10

ohm/cm. 3 165 Surface resistance VDE, 10

ohm cm. 3 165 Breakdown voltage VDE 165 Thickness of specimen: 2.05 mm.

instantaneous value, 34.5 kilovolts; 2.09 mm. after 1 min., 32 kilovolts. 3 165 Tracking resistance VDE,

stage T2, short circuit.

Example 8 A mixture of 131.1 parts of unsaturated polyester A, dissolved in 42.7 parts of ethylene chloride,

39.5 parts of bis(cyclopentadienyl) compound XI [:oligomeric bis(cyclopentadienyl) phenylmethane] dissolved in 13.2 parts of ethylene chloride,

19 parts of tertiary butylperbenzoate of 50% strength in dibutyl phthalate,

10 parts of zinc stearate,

120 parts of kaolin,

30 parts of titanium dioxide, and

150 parts of glass fibers of 6 mm. length is kneaded in 'a Werner-Pfieiderer kneader for 20 minutes and then dried for 8 hours in a vacuum cabinet at 60 C. The dried material is converted into a granulate through a 5 mm. sieve in a cutting mill, and the granulate is 18 moulded into shaped structures under a pressure of 200 kg./cm.

Molding conditions Properties Time, Temperaminutes ture, C.

8 170 Flexural strength, 662 kg./cm.

8 170 Impact strength, 4.6 cm.kg./cm.

3 170 Modulus of elasticity, 1,917

kg./m;rn.".

3 170 Absorption of cold water within 24 hours at 20 0., 0.17%.

3 170 Alasorgtion of boiling water,

3. 5 170 Dielectric loss factor tgS (50 cycles at 1,000 Volt; VDE), 0.0325.

3. 5 170 Dielectric constant 6 (50 cycles at 1,000volt; VDE) 5.0.

3. 5 170 SpecificresistanceflDE, 4.8)(10 ohm/cm.

3. 5 170 Surface resistance VDE, 10

ohm/cm.

3. 5 170 Tracking resistance VDE, stage T5, for stoved depth 0101mm.

Example 9 A mixture of 138 parts of unsaturated polyester A, dissolved in 46 parts of ethylene chloride,

32.7 parts of copolymeric bis(cy-clopen.tadienyl) compound XVI, dissolved in 11.0 parts of ethylene chloride,

19 parts of tertiary butylperbenzoate of 50% strength in dibutyl phthalate,

10 parts of zinc stearate,

parts of kaolin,

30 parts of titanium dioxide, and

parts of glass fibers of 6 mm. length is kneaded for 20 minutes in a Werner-Pfleiderer kneader and then dried for 8 hours in a vacuum cabinet at 60 C. The dried material in ground to form a granulate in a cutting mill through a 5 mm. sieve, and the granulate is moulded to form shaped products under a pressure of 200 kg./crn.

Molding conditions Properties Time,

Temperaminutes ture, C.

Flexural strength, 6810 kgJmcfl. Impact strength, 4.9 cm.kg./cm.'. Modulus 0g elasticity, 2,060

kg./mm. Absorption of cold water in 24 hours at' 20 0., 0.15%. Absorption of boiling water in 10 minutes, 0.18%. Dielectric loss factor tgs (50 cycles at 1,000 volt; VDE), 0.0425

Dielectric constant e (50 cycles at 1,000 volt; VDE), 4.4.

Specific resistance VDE, 3.2 X

10 ohm/cm.

Surface resistance VDE, 10

ohm/cm.

Tracking resistance VDE, stage T5, stoved depth 0.1 mm.

gceawwoooc Emmple 10 A mixture of 1194 parts of unsaturated polyester A, dissolved in 39.8 parts of ethylene chloride,

51.6 parts of bis(cyclopentadienyl) compound )GII [=polymeric 2:2 bis (cyclopentadienylmethyl)-spirobi-meta-dioxane] dissolved in 17.2 parts of ethylene chloride,

19 parts of tertiary butylperbenzoate of 50% dibutyl phthalate,

10 parts of zinc stearate,

120 parts of kaolin,

strength in 30 parts of titanium dioxide, and 150 parts of glass fibers of 6 mm. length is kneaded for 20 minutes in a Werner-Pfieiderer kneader and then dried for 8 hours in a vacuum cabinet at 60 C. The: dried material is converted into a granulate in a cutting mill through a 5 mm. sieve and then moulded to shaped products under a pressure of 200 kg. per cm.

Molding conditions Properties Time, Temperaminutes ture, C.

8 170 Flexural strength, 862 kg/cmfl. 8 170 Impagt strength, 7.2 cm.kg./

cm. 3 170 Modulus of elasticity, 1,900 kg./ mrnfl. 3 170 Absorption of cold water in 24 hours at 20 0., 0.20%. 170 Absorption of boiling water in 10 minutes, 0.23%. 3. 5 170 Dielectric loss factor tgfi (50 g ggilas at 1,000 volt; VDE), 3. 5 170 Dielectric constant e (50 cycles 25 at 1,000 Volt; VDE), 4,4. 3, 5 170 Specific resistance, 2.8)(10 ohm/cm. 3. 5 170 Surface resistance VDE, 10

' ohm/cm. 3. 5 170 Tracking resistance VDE, stage T5, stoved depth, 0.1 mm.

What is claimed is: 1. A curable resin composition of matter, which comprises (1) an oligomeric bis(cyclopentadienyl) compound of the formula in which R is a member selected from the group consisting of l Alkyl Aryl Si /Si\ Alkyl Aryl 2. A curable resin composition of matter, which comprises (1) an oligomeric of the formula bis(cyclopentadienyl) compound in which R is a member selected from the group consisting of Alkyl Aryl Si Si Alkyl Aryl divalent aliphatic hydrocarbon radicals, divalent cycloaliphatic hydrocarbon radicals, divalent araliphatic hydrocarbon radicals, ,divalent aliphatic hydrocarbon radicals interrupted by oxygen bridges and hydroxy-substituted divalent aliphatic hydrocarbon radicals, n is an integer of at least 2 and at the most 20, and R and R each are members selected from the group consisting of hydrogen atom and the methyl group;

(2) an unsaturated dienophilic compound in which the total number, of non-aromatic carbon-to-carbon double bonds and carbon-to-carbon triple bonds is greater than 2,

(3) as active diluent an unsaturated dienophilic com-pound in which the total number of nonaromatic carbon-to-carbon double bonds and carbon-to-carbon triple bonds is at least 1 and at the most 2.

3. A curable resin composition of matter, which comprises (1) an oligomeric bis(cyclopentadienyl) compound of the formula in which R is a member selected from the group consisting of Aryl Aryl carbon radicals, n is an integer of at least 2 and at" the most 20, and R and R each are members selected from the group consisting of hydrogen atom and the methyl group;

21 (2) an unsaturated dienophilic com-pound in which the total number of non-aromatic carbon-to-carbon double bonds and carbon-to-carbon triple bonds is greater than 2; and

(3) as catalyst a metal drier.

4. A composition as claimed in claim 1, in which the oligomeric bis(cy=c1opentadienyl) compound (1) is dimeric 1:4-bis(cyclopentadienyl)-bu.tene-2.

5. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadienyl) compound (1) is oligomeric 1 :5-bis cyclopentadienyl -pentane.

6. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadienyl) compound (1) is oligomeric 4:6-bis(cyclopentadienyl-methyl) 1:3 dimethylbenzene.

7. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadienyl) compound (1) is oligomeric 1 3-bis(cyclopentadienyl-methyl -2 4 6-trimethylbenzene.

8. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadienyl) compound (1) is dimeric 1 3-bis(cyclopentadienyl)-propanol-2.

9. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadienyl) compound (1) is dimeric di-cyclopentadienyl-dimethyl-si1ane.

10. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadienyl) compound (1) is dimeric di- (methylcyclopentadienyl -dimethylsilane.

11. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadienyl) compound (1) is dimeric di-cyclopentadienyl-diphenyl-silane.

12. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadieny1) compound (1) is oligomeric bis (cyclopentadienyl)methane.

13. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadienyl) compound (1) is olig-omeric bi s( cyclopentadienyl phenylmethane.

14. A composition as claimed in claim 1, in which the oligomeric -bis(cyclopentadienyl) compound (1) is oligomeric 1:4-bis(cyclopentadienyl)-butine-2.

15. A composition as claimed in claim 1, in which the oligomeric lbis(cyclopentadienyl) compound (1) is oligomeric 1 :4-bis'(cyclopentadienyl) cyclopentene-Z.

16. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadienyl) compound (1) is oligomeric bis(cyclopentadienyl-pentenyl)-ether.

17. A composition as claimed in claim 1, in which the oligomeric bisl(cyclopentadienyl) compound (1) is oligomeric 2:2'-bis(cyclopentadienyl)diisopropyl ether.

18. A composition as claimed in claim 1, in which the oligome-ric bis(cyclopentadienyl) compound (1) is oligomeric 2:2'-bis(cyclopentadienyl)diethyl ether.

.19. A composition as claimed in claim 1, in which the oligomeric bis(cyclopentadienyl) compound (1) is oligomeric 2 2-bis cyclopentadienyl'methyl spiro-bi-metadioxane.

20. A curable resin composition of matter, which comprises I22 (1) an oligomeric bis(cy-clopentadie'ny1) compound of the formula in which R is a member selected from the group consisting of Alkyl Aryl Alkyl Aryl divalent aliphatic hydrocarbon radicals, divalent cycloaliphatic hydrocarbon radicals, divalent araliphatic hydrocarbon radicals, divalent aliphatic hydrocarbon radicals interrupted by oxygen bridges and hydroxy-substituted divalent aliphatic hydrocarbon radicals, n is an integer of at least 2 and at the most 20, and R and R each are members selected from the group consisting of hydrogen atom and the methyl group; and

(2) an unsaturated dienophilic compound in which the total number of non-aromatic carbon-to-carbon double bonds is greater than 2.

21. A composition as claimed in claim 20, wherein the unsaturated dienophilic compound (2) is an unsaturated polyester.

22. A composition as claimed in claim 20, wherein the unsaturated dienophilic compound (2) is a polymer of a member selected from the group consisting of 'butadiene and isoprene.

23. A composition as claimed in claim 20, wherein the unsaturated dienophilic compound (2) is a copolymer of butadiene with a member selected from the group consisting of ethylene, propylene, styrene, acrylonitrile and acrylic acid esters.

24. A composition as claimed in claim 20, wherein the unsaturated dienophilic compound (2) is a copolymer of butadiene with styrene having an average molecular weight of about 8,000 to about 10,000.

25. A composition as claimed in claim 20, wherein the unsaturated dienophilic compound (2) is the triglyceride of an unsaturated fatty acid.

26. A composition as claimed in claim 20, wherein the unsaturated dienophilic compound (2) is hexamethylolmelamine-pentaallyl-ether.

No references cited.

DONALD E. CZAIA, Primary Examiner. LEON J. BERCOVITZ, Examiner. 

1. A CURABLE RESIN COMPOSITION OF MATTER, WHICH COMPRISES (1) AN OLIGOMERIC BIS (CYCLOPENTADIENYL) COMPOUND OF THE FORMULA 